CN108130225B

CN108130225B - Cleaning composition, cleaning agent, and preparation method and application thereof

Info

Publication number: CN108130225B
Application number: CN201611091079.9A
Authority: CN
Inventors: 郑翔龙; 蒋赞
Original assignee: Guangzhou Blue Moon Industrial Co ltd
Current assignee: Guangzhou Blue Moon Industrial Co ltd
Priority date: 2016-12-01
Filing date: 2016-12-01
Publication date: 2020-09-15
Anticipated expiration: 2036-12-01
Also published as: CN108130225A

Abstract

The invention discloses a microcapsule, a preparation method thereof, a cleaning composition containing the microcapsule and a cleaning agent. The cleaning composition comprises the following components by mass: 5-90 wt% of surfactant and 0.01-10 wt% of microcapsule; the microcapsule comprises hollow polymer microspheres with micro channels on the surface and a substance with fragrance and/or special odor and/or special function; the substance having a fragrance and/or a specific odor and/or a specific function is not limited by a functional group, octanol water partition coefficient (ClogP), water solubility; the surfactant in the cleaning composition is preferably a novel green environment-friendly nonionic surfactant (alcohol ether glycoside), and the surfactant and the microcapsule are compounded to obtain the green environment-friendly cleaning composition and cleaning agent with excellent performance, and are widely applied to the fields of fabric cleaning agents, tableware cleaning agents, floor cleaning agents, carpet cleaning agents, skin cleaning agents, hair cleaning agents, deodorants and the like.

Description

Cleaning composition, cleaning agent, and preparation method and application thereof

Technical Field

The invention belongs to the technical field of cleaning products, and particularly relates to a cleaning composition, a cleaning agent, and a preparation method and application thereof.

Background

The perfume components in the laundry detergent, especially those with good water solubility or low octanol water distribution coefficient (ClogP), are lost in large quantities during the fabric cleaning and rinsing processes, resulting in limited perfume retention capacity of the dried fabric, short perfume retention time, and rapid perfume loss. In order to enhance the fragrance retention capacity of clothes after being cleaned and bring wearing pleasure to people, a container capable of storing essence and releasing fragrance under specific conditions, namely essence microcapsules, is produced.

At present, emulsion polymerization, interface polymerization, in-situ polymerization, sol-gel method and the like are commonly used for preparing the essence microcapsules, and the selection of the essence microcapsules prepared by different preparation methods and wall materials can have obvious limitation. Such as: the essence microcapsules prepared by chemical methods such as emulsion polymerization, interfacial polymerization, in-situ polymerization and the like have obvious limitation on functional groups, octanol water distribution coefficient (ClogP) or water solubility of the essence, and wall materials of the essence microcapsules are represented by melamine-formaldehyde resin, urea-formaldehyde, phenol-formaldehyde, amino-formaldehyde and the like; silica or silicone oil-based perfume microcapsules prepared by a sol-gel method have obvious limitation on the polarity of a solvent for dissolving the perfume, and if the solvent commonly used for the perfume is dipropylene glycol, the solvent cannot be used. In addition, the essence microcapsules prepared by physical or physicochemical methods such as an embedding method, a spray drying method, an inclusion complex method and the like may have the defects of overlarge microcapsule particle size, limitation on essence molecule water solubility and the like, and the wall materials of the essence microcapsules are mostly represented by cyclodextrin, gelatin, modified starch, protein and the like, for example, the cyclodextrin is taken as the wall material, and the microcapsules prepared by the inclusion complex method have special requirements on the size of essence molecules; the microcapsule prepared by using hydrophilic materials such as gelatin, modified starch, protein and the like as wall materials and adopting a spray drying method has the advantages that the loss of essence and the damage of heat-sensitive substances can be caused because the preparation process needs high temperature of about 200 ℃, and the core substances in the microcapsule are easily boiled by high temperature, so that the surface of the microcapsule is in a porous structure, and the service life of the essence microcapsule is shortened. The essence microcapsules prepared by the method need to be formed into microcapsules by mixing essence with wall material solution or wall material prepolymer and then curing, so that the limitation on functional groups of core substances in the microcapsules, octanol water distribution coefficient, polarity or water solubility cannot be avoided.

CN 104919033a discloses a method for preparing ethyl vanillin or vanillin fragile shell-core microcapsule composition, the wall material is urea-formaldehyde, melamine-formaldehyde, phenol-formaldehyde or amino-aldehyde, and the prepared fragile shell-core microcapsule is mixed with ethyl vanillin or vanillin and aged, concretely, triglyceride, surfactant and the prepared shell-core microcapsule are mixed, then essence or essence dissolved in solvent (dipropylene glycol) is mixed with the above microcapsule and aged to obtain the product.

WO 99/17871 discloses a microcapsule method for encapsulating amphipathic essence, wherein the microcapsule uses hydrogel as a shell and oily substance as a core, the preparation method is based on the distribution coefficient difference of essence in an oil-water system, amphipathic essence dissolved in water can pass through the hydrogel shell and spontaneously transfer to the oily core of the microcapsule to realize essence encapsulation, and the method has limitation on the choice of essence, namely, the essence has certain solubility in both oil and water, and the essence with higher solubility in an oil phase meets the requirements.

CN 102755868A discloses microcapsules prepared from sol-gel precursor mixtures and a process for their preparation, characterized by microcapsule particles having an oil or aqueous liquid core and a shell consisting of a mixture of metal or semi-metal oxide polymers, which are preferably prepared by: combining an aqueous emulsion comprising a fragrance oil or a fragrance oil with at least one hydrolysable silicon alkoxide and curing, adding a surfactant oleyl alcohol ether-10-phosphate to the cured product, thereby preparing microcapsule particles comprising an aqueous emulsion of a fragrance oil or a fragrance oil.

In summary, in the prior art, oily components containing core substances (such as essence) and wall material prepolymers are generally used as raw materials, microcapsules are synthesized by an emulsion polymerization method, an interfacial polymerization method, an original taste polymerization method and a sol-gel method, the coated core substances are obviously limited by functional groups, octanol water distribution coefficient (ClogP), polarity and water solubility of the coated core substances, or the coated core substances are sensitive to the polarity of a solvent for dissolving the core substances, and the selectivity of the prepared microcapsules is very limited. Although there are few patented technologies to prepare microcapsules by mixing and aging a core material (e.g., essence) solution with pre-prepared microcapsules, the microcapsules are not limited by functional groups during polymerization reaction, but are still limited by octanol water distribution coefficient or hydrophilic-lipophilic balance of the core material (e.g., essence), and the mixing process must have a surfactant in cooperation with the core material and wall material system, which further increases the application limit of the coating system.

Disclosure of Invention

In order to overcome the disadvantages of the prior art, one of the objects of the present invention is to provide a microcapsule, a method for preparing the same and applications thereof, the microcapsules are universal containers which can enclose almost all substances (such as perfumes and/or mosquito repellents and/or insect repellents and/or antimicrobial agents, etc.) (hereinafter collectively referred to as first-type substances) having fragrance and/or specific odor and/or specific function used in cleaning or care compositions, are almost not limited by the functional group of the first-type substances, octanol water partition coefficient (ClogP), polarity, water solubility, are not limited by the polarity of the solvent in which the first-type substances are dissolved, and without having to find a suitable surfactant for the microcapsule-forming material to facilitate its encapsulation of the first type of substance, the first category of substance encapsulation and delivery system is a technology that has made a breakthrough.

The invention also aims to provide a cleaning composition containing the microcapsule and a preparation method and application thereof. The cleaning composition comprises microcapsules as described above, which upon cleaning are capable of being deposited onto a fabric or skin or hard surface, slowly releasing the microcapsule contents via surface microchannels, and also, upon wearing, accelerating the release of the microcapsule contents, e.g., via crushing or squeezing.

The invention also provides a cleaning agent containing the cleaning composition, and a preparation method and application thereof. The detergent may be in various forms, preferably in a liquid or solid state; the detergent may be a fabric detergent, a dish detergent, a floor detergent, a carpet detergent, a skin detergent, a hair detergent, a deodorant, etc.

The purpose of the invention is realized by the following technical scheme:

a microcapsule comprising hollow polymeric microspheres and a substance contained within the microspheres; the substance contained in the microspheres comprises a substance having a fragrance and/or having a specific odor and/or having a specific function; in addition, the hollow polymer microspheres are hollow microspheres, the shell layers are crosslinked polymers, the particle size of the microspheres is 1-300 micrometers, and the thickness of the shell layers is 0.01-100 micrometers; wherein the surface of the microsphere is provided with micro channels, and the pore diameter of the micro channels is less than or equal to 0.05 micron.

The above-mentioned "substance contained in the microspheres" is referred to as "core substance"; as previously defined, "a substance having a fragrance and/or a specific odor and/or a specific function" is described as "a first type of substance". By "special odor" is meant an odor other than "aroma". The "special functions" include mosquito repellent, insect repellent, antimicrobial, and the like.

According to the invention, the first type of substance comprises one or more of the following substances: substances with fragrance: spices, essences; substances with a special odor; substances with special functions: mosquito repellent, insect repellent, antimicrobial; and so on.

According to the invention, the first class of substances comprises one, two or three of the following three groups of substances: (1) one or more of a fragrance, an essence, or a substance having a specific odor; (2) one or more of mosquito repellent and insect repellent; (3) an antimicrobial agent.

Preferably, the first type of substance comprises one, two or three of the following three groups of substances in percentage by mass:

(1) one or more of spices, essence or substances with special odor accounts for 0-100 wt%, preferably 0.01-100 wt%, and further preferably 0.1-100 wt% of the first substance by mass percent;

(2) one or more of mosquito repellent and insect repellent accounts for 0-100 wt%, preferably 0.01-100 wt%, and more preferably 0.1-100 wt% of the first substance;

(3) the antimicrobial agent accounts for 0 to 100 weight percent of the first substance, preferably 0.01 to 90 weight percent, and also preferably 0.1 to 80 weight percent;

wherein the sum of the mass percentages of all the substances in the first substance is 100%.

According to the present invention, the microcapsules are preferably perfume microcapsules, insect-repellent microcapsules, antimicrobial microcapsules, perfume/insect-repellent microcapsules, perfume/antimicrobial microcapsules, insect-repellent/antimicrobial microcapsules or perfume/insect-repellent/antimicrobial microcapsules.

According to the present invention, other materials, noted as "second type of materials", may also be included in the core material, including but not limited to: one or more of a drug, a pesticide, a chromogen, a dye, a pigment, a flavoring agent, a sweetener, an oil, a wax, a silicone oil, a softener, a vitamin, a fat, an enzyme, a mold inhibitor, a binder, a phase change material, a flavoring agent, and the like.

According to the present invention, the core material may further include an organic solvent.

According to the invention, the first substance accounts for 0.01-100 wt%, preferably 0.1-90 wt%, more preferably 0.3-80 wt% of the core substance by mass.

According to the invention, the second substance accounts for 0-99.99 wt%, preferably 0.1-90 wt%, more preferably 0.3-80 wt% of the core substance by mass.

According to the invention, the organic solvent accounts for 0-99.99 wt%, preferably 9.9-99.8 wt%, and more preferably 19.7-99.4 wt% of the mass of the core material.

According to the present invention, the hollow polymeric microspheres have a particle size of about 1 to about 250 microns, preferably about 2 to about 100 microns, and more preferably about 3 to about 30 microns.

According to the present invention, the shell thickness of the hollow polymer microsphere is about 0.01 to 100 microns, preferably about 0.1 to 10 microns, and more preferably about 0.3 to 3 microns.

According to the present invention, the pore size of the microchannels of the hollow polymeric microspheres is less than or equal to about 0.05 microns, preferably less than or equal to about 0.03 microns, and more preferably less than or equal to about 0.02 microns.

According to the invention, the hollow polymer microspheres account for 1-99.9 wt%, preferably 20-99 wt%, and more preferably 50-95 wt% of the microcapsule by mass; the core substance accounts for 0.1-99 wt% of the microcapsule, preferably 1-80 wt%, and more preferably 5-50 wt%.

The invention further provides the following technical scheme:

a method of making a microcapsule, the method comprising: and mixing the hollow microspheres with the micro-channels with the core substance, soaking, settling and separating to obtain the microcapsule.

According to the present invention, the mixing process is performed under negative pressure, and the core material is pressed into the hollow microspheres through the microchannels of the hollow microspheres under negative pressure.

Preferably, the pressure is below 101kPa, still preferably below 30kPa, more preferably below 10 kPa.

According to the invention, the preparation method can further comprise the step of cleaning the separated microcapsules by using lower alcohol, aqueous solution or mixed solution of the lower alcohol and the aqueous solution, and washing off the core material on the surfaces of the microspheres.

According to the invention, the lower alcohol is C_1-6Alkyl alcohol, preferably C_1-4Alkyl alcohols such as methanol, ethanol, propanol or butanol, etc., more preferably ethanol.

According to the present invention, the prepared microcapsules are stored in water or an aqueous solution containing a surfactant, and stored at room temperature or low temperature.

According to the microcapsule prepared by the preparation method, the core material in the microcapsule can be slowly released through the micro-channel of the hollow microsphere in the air, the micro-channel is sealed by a water film in water or an aqueous solution containing a surfactant, and the core material in the microcapsule cannot leak into the water or the aqueous solution containing the surfactant.

According to the present invention, the hollow microsphere with a microchannel can be the hollow polymer microsphere described above, or an existing hollow microsphere with a microchannel, such as a silica microsphere with a microchannel.

According to the invention, the core material comprises the first type of material described above.

According to the present invention, the core material further comprises the above-mentioned second type of material and/or organic solvent.

According to the present invention, the organic solvent may be mixed with the first type of substance and optionally the second type of substance to form a liquid, and then mixed with the hollow microspheres.

According to the invention, the mass feed ratio of the hollow microspheres with the micro channels to the core material is 1000-0.01: 1, preferably 100-0.25: 1.

The invention also provides the following technical scheme:

a cleaning composition comprising the following components by mass: 5 to 90 wt% of a surfactant, and 0.01 to 10 wt% of the above-mentioned microcapsule.

Preferably, the composition comprises the following components by mass: 12-75 wt% of surfactant and 0.1-8 wt% of the microcapsule.

According to the present invention, the cleaning composition further comprises functional adjuncts including, but not limited to: one or more of chelating agents, preservatives, dyes, perfumes in general, builders, dye transfer inhibiting agents, enzymes, enzyme stabilizers, bleaching agents, bleach activators, clay and soil removal/anti-redeposition agents, brighteners, suds suppressors, carriers, hydrotropes, rheology modifiers, skin activators and processing aids, and the like.

The invention also provides the following technical scheme:

the preparation method of the cleaning composition comprises the following steps:

mixing the microcapsule with a surfactant to prepare the cleaning composition.

According to the present invention, the preparation method further comprises adding functional auxiliary agents to the mixture of the microcapsule and the surfactant, wherein the functional auxiliary agents include but are not limited to: one or more of chelating agents, preservatives, perfumes in general, dyes, builders, dye transfer inhibiting agents, enzymes, enzyme stabilizers, bleaching agents, bleach activators, clay and soil removal/anti-redeposition agents, brighteners, suds suppressors, carriers, hydrotropes, rheology modifiers, skin activators and processing aids, and the like.

The invention further provides the following technical scheme:

a cleaning agent, which comprises the cleaning composition.

According to the invention, the addition amount of the cleaning composition in the cleaning agent is 15-90 wt%.

According to the invention, the cleaning agent may be in various forms, preferably in liquid or solid form.

According to the present invention, when the cleaning agent is in a liquid state, the balance of the cleaning agent is a solvent, such as deionized water.

According to the present invention, when the cleansing agent is solid, the remaining component in the cleansing agent is a filler for molding the same.

Preferably, the filler is one or more of sodium sulfate decahydrate, sodium carbonate, sodium silicate, 4A zeolite, and the like.

According to the invention, the cleaning agent also comprises a pH regulator.

Preferably, the pH adjusting agent is selected from citric acid, hydrochloric acid, sodium hydroxide, sodium carbonate, monoethanolamine, triethanolamine, and the like.

According to the invention, the pH of the cleaning agent is 5-13.

Preferably, the pH of the cleaning agent is 5.5-13. When the cleaning agent is in a liquid state, the pH value is more preferably 5.5-9. When the detergent is solid, the pH is more preferably 9 to 11.

In the invention, the cleaning agent has the effects of decontamination, long-acting fragrance retention, mosquito repelling and microorganism resisting in a wider pH range; however, the detergent is too alkaline to easily irritate the skin or textile fibers of a user and cause damage to the skin or textile, and therefore, the detergent can be selected within the above range according to actual use.

The invention further provides the following technical scheme:

a method of preparing a liquid detergent, the method comprising: mixing and dissolving the components in the cleaning composition in a solvent, adjusting the pH of the mixed solution to 5.5-9, adding the solvent to 100 wt%, and uniformly stirring to obtain the liquid cleaning agent.

A method of making a solid detergent, such as a powdered or granular detergent, comprising: mixing and grinding (such as grinding in a colloid mill) the surfactant, the filler and the optional functional auxiliary agent in the cleaning composition to prepare slurry with the solid content of 50-60 wt%, diluting with water, adjusting the pH value to 9-11, sieving turbid liquid, then spray-drying, sieving, adding the microcapsule, and uniformly mixing to obtain the solid cleaning agent.

A method of making a solid detergent, such as a block detergent, comprising: mixing and grinding (such as grinding in a colloid mill) the surfactant, the filler and the optional functional auxiliary agent in the cleaning composition to prepare slurry with the solid content of 50-60 wt%, diluting with water, adjusting the pH value to 9-11, sieving turbid liquid, adding the microcapsules, uniformly mixing, and curing and forming to obtain the solid cleaning agent.

Compared with the prior art, the invention has the following beneficial effects:

1. the invention provides a microcapsule and a preparation method and application thereof. With the microcapsules of the present invention and the preparation method of the present invention, the core material selected is not limited by the functional group, octanol water partition coefficient (ClogP), polarity, and water solubility, so that microcapsules having a fragrance and/or having a specific odor and/or having a specific function (e.g., essence, perfume, a substance having a specific odor, insect repellent, mosquito repellent, antimicrobial) can be obtained by the preparation method.

2. The invention also provides a cleaning composition and a cleaning agent containing the microcapsule, and a preparation method and application thereof. The microcapsules prepared by the method are added into a detergent system, and the microcapsules can be deposited on the surface of a substance to be cleaned (such as fabric, skin, hard surface and the like) in a physical adsorption or chemical adsorption mode in the cleaning process. The surface of the microcapsule selected by the invention is provided with micro-channels, volatile core substances (such as spices, essences, substances with special odor, insect repellents and mosquito repellents) in the microcapsule can be slowly released through the micro-channels in the air, the micro-channels on the surface of the microcapsule are sealed by a water film in water or an aqueous solution containing a surfactant, and the core substances in the microcapsule cannot leak into the water or the aqueous solution containing the surfactant. In addition, the shell layer of the microcapsule is composed of cross-linked polymer, and can be a brittle shell layer or an elastic shell layer, and the release of the core substance in the microcapsule can be accelerated in the air by means of shell layer rupture, and also can be accelerated by means of shell layer extrusion deformation, so that the core substance in the microcapsule can be delivered in various ways within a desired time.

3. The surfactant added into the cleaning composition provided by the invention is selected from easily biodegradable alkyl ester quaternary ammonium salt and novel green environment-friendly nonionic surfactant (such as alcohol ether glucoside), the cleaning composition obtained by compounding the surfactant and the microcapsule has better stability, can keep fragrance for a long time, is more green and environment-friendly, and is widely applied to the fields of fabric cleaning agents, tableware cleaning agents, floor cleaning agents, carpet cleaning agents, skin cleaning agents, hair cleaning agents, deodorant and the like.

Detailed Description

[ hollow Polymer microspheres and preparation thereof ]

As mentioned above, the microcapsule of the present invention comprises a hollow polymer microsphere, wherein the hollow polymer microsphere is a hollow microsphere, the shell layer is a crosslinked polymer, the particle size of the microsphere is 1 to 300 micrometers, and the thickness of the shell layer is 0.01 to 100 micrometers; wherein the surface of the microsphere is provided with micro channels, and the pore diameter of the micro channels is less than or equal to 0.05 micron.

In the present invention, the particle size of the hollow polymer microspheres is about 1 to 250 micrometers, preferably about 2 to 100 micrometers, and more preferably about 3 to 30 micrometers.

In the invention, the shell thickness of the hollow polymer microsphere is about 0.01 to 100 microns, preferably about 0.1 to 10 microns, and more preferably about 0.3 to 3 microns.

In the present invention, the pore size of the microchannels of the hollow polymeric microspheres is less than or equal to about 0.05 microns, preferably less than or equal to about 0.03 microns, and more preferably less than or equal to about 0.02 microns.

The shell layer of the hollow polymer microsphere with the micro-channels on the surface is composed of a cross-linked polymer, and is preferably a brittle shell layer or an elastic shell layer.

The hollow polymer microspheres with microchannels on the surface of the brittle shell layer are disclosed in the patent application entitled "a hollow polymer brittle microspheres with microchannels on the surface and a preparation method and application thereof", which is filed on the same day by the applicant, and the whole content of the patent application is incorporated as the disclosure of the invention.

In the present invention, "brittle" means: the property of the microspheres that the microspheres break and break under the action of external force; in particular, the property of the microspheres that only a small deformation, i.e., fracture failure, occurs under a certain external force is called brittleness.

The hollow polymer brittle microspheres with the micro-channels on the surfaces have the characteristic of being fragile, wherein the fragile refers to the tendency of the microspheres to break when physical force such as extrusion or friction is applied, and the core material in the microcapsules can be released in an accelerated manner by breaking the fragile shell layers.

The polymerization monomer for forming the cross-linked polymer in the brittle shell layer is one or more of styrene and alkyl (methyl) acrylate. Preferably, the alkyl (meth) acrylate is selected from C (meth) acrylic acid_1-4One or more alkyl esters, preferably one or more methyl methacrylate, ethyl methacrylate, methyl acrylate and ethyl acrylate. Also preferably, the polymerized monomer is one or more of styrene, methyl acrylate and methyl methacrylateTwo kinds of the above-mentioned materials, or a mixture of one or two kinds of styrene, methyl acrylate and methyl methacrylate and one or two kinds of ethyl acrylate and ethyl methacrylate respectively. The crosslinking agent of the crosslinked polymer is one or more of divinylbenzene, cyclopentadiene, dicyclopentadiene, and methylcyclopentadiene.

The hollow polymer microspheres with microchannels on the surface of the elastic shell layer are disclosed in the patent application entitled "hollow polymer elastic microspheres with microchannels on the surface and preparation method and application thereof", which is filed on the same day by the applicant, and the whole content of the patent application is incorporated as the disclosure of the invention.

In the present invention, "elastic" means: the microspheres have the characteristic of elastic restorability, namely, the microspheres deform under the action of an external force, but can be restored to the shape before deformation after the external force is removed.

The hollow polymer elastic microspheres with the micro channels on the surfaces have the characteristics of easy deformation and recoverable deformation but not easy breakage when being extruded or rubbed, and the core substance in the microcapsules can be released in an accelerated manner by the extrusion deformation of the elastic shell layers.

The polymerized monomers forming the crosslinked polymer in the elastic shell layer comprise a monomer A and a monomer B, wherein the monomer A is a monomer for making the crosslinked polymer brittle, and the monomer B is a monomer for making the crosslinked polymer elastic. Preferably, the monomer A comprises one or more of styrene, methyl methacrylate and methyl acrylate; the monomer B comprises methacrylic acid C_3-5Alkyl esters, acrylic acid C_3-5One or more of alkyl esters. Further preferably, the monomer B comprises methacrylic acid C₄Alkyl esters, acrylic acid C₄Alkyl esters, including C₄Various isomers of alkyl groups, such as n-butyl methacrylate and n-butyl acrylate. The crosslinking agent of the crosslinked polymer is one or more of divinylbenzene, cyclopentadiene, dicyclopentadiene, and methylcyclopentadiene.

The polymerized monomers of the crosslinked polymer may further comprise a monomer C, wherein the monomer C is a monomer that adjusts the elasticity and/or brittleness of the crosslinked polymer. Preferably, the monomer C includes one or both of ethyl methacrylate and ethyl acrylate.

The crosslinked polymer comprises, by weight, 20 wt% or more and less than 80 wt% of monomer A and 20 wt% or more and less than 80 wt% of monomer B. Preferably, the crosslinked polymer comprises, by weight, more than or equal to 30 wt% and less than 70 wt% of monomer A, more than or equal to 30 wt% and less than 70 wt% of monomer B and more than 0 and less than or equal to 60 wt% of monomer C based on the mass of the polymer.

In a preferred embodiment of the present invention, the method for preparing the hollow polymeric microspheres comprises the steps of: 1) preparing an oil-in-water type micro-droplet suspension; 2) preparing a mixed solution containing a polymerization monomer, a cross-linking agent and an initiator; 3) dripping the mixed solution obtained in the step 2) into the suspension obtained in the step 1) at a certain temperature, reacting, and forming a cross-linked polymer shell layer on the surface of the micro-droplet; 4) regulating and controlling the temperature of the reaction system and reacting for a certain time at the temperature to obtain the hollow polymer microsphere with the micro-pore channels on the surface.

The method further comprises the steps of:

5) the product of step 4) is further processed as follows: and (4) flotation and drying.

Wherein, the step 1) is specifically as follows: firstly, adding an organic solvent into an aqueous phase system, dispersing the organic solvent in the aqueous phase system under stirring, gradually heating to prepare an oil-in-water type micro-droplet suspension; wherein the aqueous phase system is an aqueous solution dissolved with a colloid protective agent. Wherein the colloid protective agent is polyvinyl alcohol. Still preferably, in the aqueous phase system, the mass percentage of the colloid protective agent is 0.5-5.0 wt%. Wherein the organic solvent is one of n-hexane, cyclohexane, n-heptane, isooctane and methylcyclohexane.

In the step 2), the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile and benzoyl peroxide, and the amount of the initiator is 1-3 wt% of the total mass of the polymerization monomer and the cross-linking agent.

And 4), after the reaction is finished, cooling the system to room temperature, filtering, washing, air-drying and vacuum-drying to obtain the hollow polymer microsphere.

Wherein, the flotation in the step 5) is lower alcohol soaking and sedimentation. The step 5) is specifically as follows: dispersing the hollow polymer microspheres obtained in the step 4) in lower alcohol, stirring the mixture for indefinite time, precipitating a part of the microspheres floating on the liquid level of the lower alcohol to the bottom of the container, filtering the mixture after the precipitation is completed, and air-drying and vacuum-drying the floating microspheres at the upper part to obtain the final hollow polymer microspheres. In the step 5), the stirring is specifically performed at a rotation speed of 300-400 rpm for 5-20 minutes (e.g., 10 minutes) every 1-2 hours, the operation is continuously performed for 10-15 times (e.g., 12 times), and then the mixture is allowed to stand for 12-36 hours (e.g., 24 hours). Wherein the lower alcohol is C_1-6Alkyl alcohol, preferably C_1-4Alkyl alcohols such as methanol, ethanol, propanol or butanol, etc., preferably ethanol.

In the preparation process of the hollow polymer brittle microspheres:

in step 1), gradually raising the temperature and making the system temperature (T)₁) Stabilized below the boiling point (T) of the organic solvent₀) A temperature of 12 to 40 ℃ i.e. T₀(℃)-T₁(DEG C) 12-40 ℃. Preferably, T₀(℃)-T₁(DEG C) 15-35 (DEG C); also preferably, T₀(℃)-T₁(℃)＝15～30(℃)。

In step 3), the reaction temperature (T)₂) Controlled below the boiling point (T) of the organic solvent₀) A temperature of 12 to 40 ℃ i.e. T₀(℃)-T₂(DEG C) 12 to 40 (DEG C), preferably T₀(℃)-T₂(DEG C) 15 to 35 (DEG C), and further preferably T₀(℃)-T₂(DEG C) 15-30 (DEG C); the reaction time is 0.5 to 4 hours, preferably 0.5 to 2 hours.

In step 4), the temperature (T) of the reaction system is controlled₃) To below the boiling point (T) of the organic solvent₀) A temperature of 0 to 10 ℃ i.e. T₀(℃)-T₃The reaction is carried out at 0 to 10 ℃ and the reaction is carried out at the temperature for 1 to 6 hours, preferably 2 to 4 hours.

In the preparation process of the hollow polymer elastic microspheres:

in step 1), gradually raising the temperature and making the system temperature (T)₁) Stabilized below the boiling point (T) of the organic solvent₀) A temperature of 16 to 40 ℃ i.e. T₀(℃)-T₁(DEG C) 16-40 ℃. Preferably, T₀(℃)-T₁(DEG C) 16-35 (DEG C); also preferably, T₀(℃)-T₁(℃)＝16～30(℃)。

In step 3), the reaction temperature (T)₂) Controlled below the boiling point (T) of the organic solvent₀) A temperature of 16 to 40 ℃ i.e. T₀(℃)-T₂16 to 40 (DEG C), preferably T₀(℃)-T₂(DEG C) 16 to 35 (DEG C), and further preferably T₀(℃)-T₂(DEG C) 16-30 (DEG C); the reaction time is 0.5 to 4 hours, preferably 0.5 to 2 hours.

In step 4), the temperature (T) of the reaction system is controlled₃) To below the boiling point (T) of the organic solvent₀) A temperature of 5 to 15 ℃ i.e. T₀(℃)-T₃The reaction is carried out at 5 to 15 ℃ and the reaction is carried out at the temperature for 1 to 6 hours, preferably 2 to 4 hours.

In a preferred embodiment of the present invention, the preparation method of the hollow polymer brittle microspheres comprises: adding a certain amount of 0.5-5.0 wt% of distilled water protective colloid solution and an organic solvent into a reactor provided with a stirrer and a reflux condensing device in sequence, adjusting the stirring speed to be 300-3000 rpm, stirring for 10 minutes at room temperature, starting heating and stabilizing the temperature of the system to be 15-30 ℃ lower than the boiling point of the organic solvent. Placing a monomer with the mass of 30-100 wt% of the mass of the organic solvent and a cross-linking agent with the mass of 50-100 wt% of the mass of the monomer into a beaker, adding an initiator with the mass of 1-3 wt% of the total mass of the monomer and the cross-linking agent, and stirring until the initiator is completely dissolved to form a uniform mixed solution. And (3) dropwise adding the newly prepared monomer, initiator and cross-linking agent mixed solution into the system, and keeping the temperature to continuously react for 0.5-2 hours after dropwise adding. The temperature of the system is raised to 5-15 ℃ lower than the boiling point of the organic solvent, and then the reaction is carried out for 2-4 hours. And then cooling the system to room temperature, and filtering, cleaning, air drying and vacuum drying to obtain the hollow polymer microspheres with the surface microchannels communicated with the inner cavities. Dispersing the prepared hollow polymer microspheres in a beaker filled with ethanol, stirring the hollow polymer microspheres at variable time, slowly settling a part of the microspheres floating on the liquid level of the ethanol to the bottom of the beaker, filtering the mixture after the microspheres are completely settled, and air-drying and vacuum-drying the floating microspheres on the upper part of the beaker to obtain the hollow polymer fragile microspheres with better connectivity between the surface micro-channels and the internal cavities.

In a preferred embodiment of the present invention, the method for preparing the hollow polymer elastic microspheres comprises: adding a certain amount of 0.5-5.0 wt% of distilled water protective colloid solution and an organic solvent into a reactor provided with a stirrer and a reflux condensing device in sequence, adjusting the stirring speed to be 200-1500 rpm, stirring for 10 minutes at room temperature, starting heating and stabilizing the temperature of the system at 15-30 ℃ below the boiling point of the organic solvent. Putting a polymerization monomer with the mass of 60-150 wt% of the organic solvent and a cross-linking agent with the mass of 20-50 wt% of the polymerization monomer into a beaker, adding an initiator with the mass of 1-3 wt% of the total mass of the polymerization monomer and the cross-linking agent, and stirring until the initiator is completely dissolved to form a uniform mixed solution. And (3) dropwise adding the newly prepared monomer, initiator and cross-linking agent mixed solution into the system, and keeping the temperature to continuously react for 0.5-2 hours after dropwise adding. The temperature of the system is increased to 10-15 ℃ lower than the boiling point of the organic solvent, and then the reaction is carried out for 2-4 hours. And then cooling the system to room temperature, and filtering, cleaning, air drying and vacuum drying to obtain the hollow polymer microspheres with the surface microchannels communicated with the inner cavities. Dispersing the prepared hollow polymer microspheres in a beaker containing alcohol, stirring the hollow polymer microspheres at variable time, slowly settling a part of the microspheres floating on the alcohol liquid level to the bottom of the beaker, filtering the mixture after the microspheres are completely settled, and air-drying and vacuum-drying the floating microspheres on the upper part of the beaker to obtain the hollow polymer elastic microspheres with better connectivity between the surface micro-channels and the internal cavities.

[ core Material ]

As previously mentioned, the microcapsules of the present invention comprise hollow polymeric microspheres and a substance contained in the microspheres; the "substance contained in the microspheres" is referred to as "core substance".

In the present invention, the core material includes a material having a fragrance and/or a specific odor and/or a specific function, which is denoted as "first type material".

In the present invention, the core material may further comprise other materials, which are referred to as "second type materials".

In the present invention, the core material may further include an organic solvent.

In the present invention, the core material is not limited by the functional group, octanol water partition coefficient (ClogP), polarity, and water solubility, and may be a component having a single chemical structure or a mixture of one or more components.

[ first class of substances ]

As mentioned above, the microcapsules of the present invention comprise a first type of substance, which comprises one or more of the following substances: substances with fragrance: spices, essences; substances with a special odor; substances with special functions: mosquito repellent, insect repellent, antimicrobial; and so on.

The first substance is not limited by functional groups, octanol water partition coefficient (ClogP), polarity, and water solubility, and may be a component having a single chemical structure or a mixture of more than one component.

Scented and special scent materials suitable for use in the present invention include, but are not limited to: herbal fragrances such as peppermint, spearmint, rosemary, thyme, sage and atomic pine, spruce and other trees with forest odors; fruit scents such as apple, almond, grape, cherry, pineapple, pear, honey peach, mango, orange, strawberry, blueberry, citrus; floral scents, such as rose-like, lavender-like, carnation-like; and vanilla, gardenia, hawthorn, white cabbage, honeysuckle, cyclamen, hyacinth, bracken, clove, jasmine, lily, mimosa, magnolia, orchid, narcissus, orange blossom, licorice, reseda green, clover, violet, sweet pea, wallflower, etc. (Perfumes Cosmetics and Soaps, "second edition, published by w.a. poucher in 1959).

Odoriferous and special odoriferous substances having an octanol water partition coefficient ClogP of greater than or equal to 3.4 suitable for use in the present invention include, but are not limited to: geraniol acetate, linalool acetate, carvacrol, isobornyl acetate, tetrahydromyrcenol, ylacene, vetiveryl acetate, musk forth, musk pink, musk indanone, alpha-santalol, phenyl heptanol, phenylethyl benzoate, phenylethyl phenylacetate, 10-oxahexadecanolide, 11-oxahexadecanolide, 1- (1, 1-dimethylethyl) -3,4, 5-trimethoxy-2, 6-dinitrobenzene, g-n-ionone, methyl dihydrojasmone, linalyl benzoate, alpha-irilone, hexyl salicylate, cyclohexyl salicylate, hexenyl salicylate, hexyl cinnamaldehyde, hexadecanolide, geranyl phenylacetate, geranyl anthranilate, ethyl undecylenate, dodecalactone, ethyl crotonoate, ethyl crotonoxide, methyl-leucyl salicylate, and mixtures thereof, Diphenyl ether, diphenylmethane, cyclamen aldehyde, cinnamyl cinnamate, cedryl formate, cedryl acetate, ethyl acetoacetate, methylhexylagaldehyde, benzyl propionate, cedrol, cadinene, beta-caryophyllene, isobutylquinoline, p-tert-butylcyclohexylacetate, benzyl salicylate, isoamyl salicylate, amyl cinnamaldehyde dimethyl acetal, amyl cinnamate, amyl benzoate, muscolide, allyl cyclohexanepropionate and the like.

Odoriferous and special odor materials having an octanol water partition coefficient ClogP of less than 3.4 suitable for use in the present invention include, but are not limited to: coumarin, vanillin, eugenol, isoeugenol, methyl cinnamate, beta-methyl-naphthalenyl ketone, d-undecanolactone, vanillin, methyl dihydrojasmonate, dihydromyrcenol, geraniol, levocitronellol, dextrocitronellol, racemic citronellol, hydroxycitronellal, lilial, linalool, benzyl acetate, benzaldehyde, levocarvone, nerol, linalool, phenethyl alcohol, phenylhexanol, alpha-terpineol, myristyl ether, muscone, and the like.

Preferably, the odoriferous substance and the substance having a distinctive odor may be selected from one or more of phenethyl alcohol, hexyl cinnamic aldehyde, levo citronellol, dextro citronellol, terpineol, hydroxycitronellal, lilial, linalool, geraniol, vanillin, ethyl acetate, ethyl acetoacetate, benzyl acetate, dihydromyrcenol, methyl hexyl cinnamic aldehyde, benzyl propionate, g-n-ionone.

The above-mentioned preferably odoriferous substances and substances with special odors have good volatility and provide good flavor effects and flavor experience when used as a main fragrance. Furthermore, when the above-mentioned preferably odorous substances and substances having a special odor are used in combination with the hollow polymer microspheres of the present invention, the odorous substances and/or substances having a special odor and/or substances having a special function, which are wrapped inside the hollow polymer microspheres, may be slowly released through the microchannels when in the air; when in water or an aqueous solution containing a surfactant, the micro-channels on the surface of the hollow polymer microspheres are sealed by a water film, and the substances with fragrance and/or substances with special odor and/or special functions in the micro-channels do not leak into the water or the aqueous solution containing the surfactant.

In the present invention, the octanol water partition coefficient ClogP of the substances with fragrance and the substances with special odor can be more than or equal to 3.4 or less than 3.4, and the mixture can provide multi-level perfume effect and fragrance experience.

Preferably, the odoriferous substance and the odor-specific substance suitable for the present invention may be selected from one or more of the odoriferous substance and the odor-specific substance having an octanol water partition coefficient ClogP of greater than or equal to 3.4, from one or more of the odoriferous substance and the odor-specific substance having an octanol water partition coefficient ClogP of less than 3.4, and from a combination of one or more of the odoriferous substance and the odor-specific substance having an octanol water partition coefficient ClogP of greater than or equal to 3.4 and one or more of the odoriferous substance and the odor-specific substance having an octanol water partition coefficient ClogP of less than 3.4.

In the invention, the mosquito repellent and insect repellent include but are not limited to: the mosquito repellent composition is prepared by using DEET, Icaritin (Icaridin), anophelate, menthol and natural mosquito repellents (such as sweet wormwood essential oil, eucalyptus essential oil, chinaberry oil and the like), preferably using the DEET with good mosquito repellent effect as an insect repellent microcapsule in a floor cleaner, and preferably using the Icaritin (Icaridin) without irritation to skin as an insect repellent microcapsule in a skin surface cleaner.

In the present invention, the antimicrobial agents include, but are not limited to: isothiazolone derivatives (e.g., 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, etc.), parabens (e.g., methyl paraben, ethyl paraben, propyl paraben, butyl paraben, isobutyl paraben, etc.), 1, 2-benzisothiazolin-3-one, hexachlorophene, sodium hydroxymethylglycinate, preferably isothiazolone derivatives are used as antimicrobial microcapsules in detergents.

In the present invention, the perfume, essence, special odor substance, mosquito repellent, insect repellent, antimicrobial agent suitable for the present invention may be selected from a single component or a mixture of more than one component, and preferably, the mixture of one or more of the perfume, essence, special odor substance and one or more of insect repellent, antimicrobial agent is selected.

As mentioned above, the core material of the present invention can comprise a single component, and can also comprise more than two components, thereby solving the defects of single material and single function in the microcapsule in the prior art. It is known in the art of cleaning that, in addition to the introduction of a substance having a fragrance, clothes are liable to develop an offensive odor during wearing or after wearing, which is generated by the action of microorganisms by sweat gland secretions of a human body attached to the clothes, microcapsules containing an antimicrobial agent such as an antibacterial agent, which remain on the clothes and are capable of ensuring the release of the antimicrobial agent under specific conditions (e.g., during a large amount of exercise) to inhibit the generation of bacteria, thereby effectively inhibiting the generation of the offensive odor. Furthermore, natural ingredients or synthetic compounds for repelling or controlling mosquitoes are stored in the microcapsule, and the microcapsule is added into a skin surface cleaning agent or a hard surface cleaning agent (such as a floor cleaning agent), the microcapsule can be remained on the surface after cleaning is finished, and the effective ingredients in the microcapsule are released in some modes, so that the purpose of repelling the mosquitoes is achieved. The microcapsule of the invention can wrap the substances with various functions or smells and realize effective release, thereby having very good application prospect.

[ second class of substances ]

As previously mentioned, the microcapsules of the present invention may contain a second class of materials, including but not limited to: one or more of a drug, a pesticide, a chromogen, a dye, a pigment, a flavoring agent, a sweetener, a fragrance, an oil, a wax, a silicone oil, a softener, a vitamin, a fat, an enzyme, a mold inhibitor, a binder, a phase change material, a flavoring agent, and the like.

The second substance is not limited by a functional group, octanol water partition coefficient (ClogP), polarity, and water solubility, and may be a component having a single chemical structure or a mixture of one or more components.

In the present invention, the second type of substance and the addition amount thereof are routine choices for those skilled in the art; when the second type of substance is further introduced into the microcapsule, the functions of the microcapsule can be increased, but the functions of other core substances in the microcapsule and the overall performance of the microcapsule are not influenced.

[ organic solvent ]

As mentioned above, the microcapsules of the present invention may contain organic solvents, including but not limited to: one or more of ethanol, dipropylene glycol, isopropanol, diethylene glycol, propylene glycol, monoethyl ether, diethyl phthalate, dibutyl phthalate, triethyl citrate, and the like.

In the present invention, the organic solvent is uniformly mixed with the first type of substance and optionally the second type of substance, and then encapsulated in the microcapsule together.

In the present invention, the addition of the organic solvent makes it possible to adjust the concentration of the first type of substance and optionally of the second type of substance and the density of the microcapsules.

In the present invention, the amount of the organic solvent added is preferably kept at the minimum amount required to provide a uniform solution of the first type of substance and/or the second type of substance, and an appropriate amount to adjust the density of the microcapsules.

[ preparation of microcapsules ]

The invention also provides a preparation method of the microcapsule, which comprises the following steps: mixing the hollow microspheres with the micro-channels with a core substance, soaking, settling and separating to obtain the microcapsule.

In a preferred embodiment of the present invention, the method for preparing the microcapsule specifically comprises the following steps:

a) mixing the first kind of substance and the optional second kind of substance with an organic solvent to obtain a liquid core substance, and mixing, soaking and settling hollow microspheres with micro-channels with the core substance under negative pressure;

b) separating the microspheres settled in the step a), and cleaning core substances on the surfaces of the microspheres by using lower alcohol, aqueous solution or mixed solution of the lower alcohol and the aqueous solution to prepare the microcapsules.

a') placing hollow microspheres with micro-channels in a single-opening glass container with an air extraction joint, mixing the first type of substance and optionally the second type of substance with an organic solvent to form a liquid core substance, placing the liquid core substance in a constant-pressure dropping funnel, assembling the constant-pressure funnel and the single-opening glass container, connecting a vacuum air extraction device, and extracting air for 5-120 minutes; under the negative pressure lower than 30kPa, a constant-pressure funnel switch is opened, so that the core substance in the funnel is mixed with the microspheres in the container, soaked and settled;

b') separating the settled microspheres, and washing the surfaces of the microspheres by using a proper solvent, such as ethanol or water or a mixed solution of ethanol and water to obtain the microcapsules.

[ cleaning composition ]

As previously mentioned, the cleaning composition of the present invention comprises the following components by mass: 5 to 90 wt% of a surfactant, and 0.01 to 10 wt% of the above-mentioned microcapsule.

The cleaning compositions also contain functional adjuncts which are not essential to applicants' cleaning compositions, but functional adjunct materials exemplified below are suitable for use in the compositions of the present invention and may be desirably incorporated into certain embodiments of the invention, including but not limited to: one or more of chelating agents, preservatives, dyes, perfumes in general, builders, dye transfer inhibiting agents, enzymes, enzyme stabilizers, bleaching agents, bleach activators, clay and soil removal/anti-redeposition agents, brighteners, suds suppressors, carriers, hydrotropes, rheology modifiers, skin activators and processing aids, and the like.

The surfactant is an anionic surfactant or a mixture of an anionic surfactant and a surfactant other than a cationic surfactant.

The surfactant is preferably a mixture of an anionic surfactant and a nonionic surfactant, a mixture of an anionic surfactant and a zwitterionic surfactant, or a mixture of an anionic surfactant and a nonionic surfactant and an amphoteric surfactant.

When the selected anionic surfactant is compounded with a surfactant except the cationic surfactant, the mass percentage of the anionic surfactant in the mixture is 20-90 wt%, preferably 40-85 wt%.

When anionic surfactants are selected to be complexed with surfactants other than cationic surfactants, the soil removal and anti-redeposition abilities are greater than when anionic surfactants, zwitterionic surfactants or nonionic surfactants are used alone.

The anionic surfactant can be selected from carboxylate type, sulfate type and sulfonate type surfactants. Preferably, the anionic surfactant includes alcohol ether carboxylate, alkyl sulfate, alkyl ethoxylated sulfate, alkyl benzene sulfonate, fatty alcohol sulfate, fatty alcohol sulfonate, fatty alcohol ether sulfate, alpha-alkenyl sulfonate, fatty acid methyl ester ethoxylated sulfonate, and the like, and preferably includes alkyl benzene sulfonate, alkyl ethoxylated sulfate, and alpha-alkenyl sulfonate.

The nonionic surfactant can be selected from alkyl glucoside, alkyl alcohol ether glucoside, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyalkylene fatty acid ester, fatty acid alkanolamide or N-alkyl-2-pyrrolidone, etc. Preferred are polyoxyethylene alkyl ethers, alkyl alcohol ether glucosides and N-alkyl-2-pyrrolidones, and further preferred are alkyl alcohol ether glucosides.

The zwitterionic surfactant can be selected from alkyl betaine, alkyl hydroxysultaine, alkyl amidopropyl betaine, alkyl amidopropyl hydroxysultaine, alkyl ammonium oxide, carboxylic acid type imidazoline, etc., preferably alkyl amidopropyl betaine and alkyl hydroxysultaine.

Preferably, the length of the alkyl carbon chain in the anionic surfactant, the nonionic surfactant and the zwitterionic surfactant is C₁₀～C₁₈In the meantime.

The anionic surfactant or the amphoteric surfactant contains counter ions with opposite electric properties, and the optional counter ions are selected from one or more of potassium ions, sodium ions, ammonium ions, alcohol amine ions and hydrogen ions.

[ functional auxiliary in cleaning composition ]

Chelating agent in the present invention, the chelating agent is selected from aminocarboxylic acid compounds and/or organic aminophosphonic acid compounds and/or sodium citrate, the aminocarboxylic acid compounds including but not limited to: ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DEPTA); such organo aminophosphonic acid compounds include, but are not limited to: ethylenediaminetetra (methylenephosphonic acid), 1-hydroxyethane 1, 1-diphosphonic acid (HEDP) and aminotri (methylenephosphonic acid). If chelating agents are used, these chelating agents are generally present in an amount of 0.1 to 15 wt.%, preferably 1 to 15 wt.%, based on the weight of the cleaning composition.

[ antiseptic ] in the present invention, the antiseptic is one selected from the group consisting of carbone (a mixture of 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one), 2-methyl-4-isothiazolin-3-one, and 5-chloro-2-methyl-4-isothiazolin-3-one. If preservatives are used, these are generally present in an amount of 0.01 to 1 wt.%, preferably 0.02 to 0.2 wt.%, based on the mass of the cleaning composition.

Dyes in the present invention, the dyes are selected from direct dyes in an amount sufficient to provide coloration, and suitable dyes include, but are not limited to: acid dyes of various colors, basic dyes of various colors, and sodium salts of mixtures of mono-and disulfonic acids of 4-nitrophthalenediamine, 2-nitrophenylenediamine, 4-amino-3-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 4-nitrophenylglycine urea, 6-nitro-2, 5-pyridinediamine, quinophthalone or 2-indenedione, 2-hydroxy-1, 4-naphthoquinone, henna, indigo, cochineal and mixtures thereof. If dyes are used, the content of the dyes is generally 0.01 to 5 wt% of the cleaning composition by mass.

Conventional perfume in the present invention, the conventional perfume is selected from the group of perfumes described hereinbefore and mixtures thereof, including but not limited to mixtures of one or more of perfumes having an octanol water partition coefficient ClogP of less than 3.4 and one or more of perfumes having an octanol water partition coefficient ClogP of 3.4 or more, preferably mixtures of a plurality of perfumes having an octanol water partition coefficient ClogP of less than 3.4 and a plurality of perfumes having an octanol water partition coefficient ClogP of 3.4 or more, to provide a pleasant or impressive fragrance experience. If conventional perfumes are used, the amount of these perfumes is generally 0.01 to 5 wt%, preferably 0.05 to 2 wt%, based on the mass of the cleaning composition.

Builder the builder is typically used in solid detergents in the present invention and is selected from sodium silicate and 4A molecular sieves, and mixtures thereof. If builders are used, these builders are generally present in an amount of from 0.1 to 50 wt.%, preferably from 1 to 35 wt.%, based on the mass of the cleaning composition.

[ dye transfer inhibiting agent ] in the present invention, the dye transfer inhibiting agent is selected from the group consisting of polyvinylpyrrolidone, polyamine N-oxide, copolymer of N-vinylpyrrolidone-N-vinylimidazole, polyvinylimidazole, polyvinyloxazolidone, and a mixture thereof. If dye transfer inhibitors are used, these are generally present in an amount of 0.01 to 10 wt.%, preferably 0.1 to 5 wt.%, based on the mass of the cleaning composition.

In the present invention, the enzyme is selected from the group consisting of protease, cellulase, lipase, amylase, pectinase, xylanase, oxidase, reductase, peroxidase, and a mixture thereof, and a typical combination thereof is one or a mixture of more than one of protease, cellulase, amylase, and lipase. If enzymes are used, the content of these enzymes is usually 0.01 to 15 wt%, preferably 0.1 to 10 wt% of the cleaning composition.

Enzyme stabilizer in the present invention, the enzyme stabilizer is selected from the group consisting of calcium chloride, calcium formate, calcium gluconate, and a mixture thereof. If enzyme stabilizers are used, these are generally present in an amount of 0.001 to 5 wt.%, preferably 0.005 to 3 wt.%, based on the mass of the cleaning composition.

Bleaching agent in the present invention, the bleaching agent is selected from sodium percarbonate, encapsulated sodium percarbonate, hydrogen peroxide, sodium hypochlorite and mixtures thereof, preferably sodium percarbonate and encapsulated sodium percarbonate and mixtures thereof. If bleaching agents are used, these are generally present in an amount of 0.01 to 15 wt.%, preferably 0.1 to 15 wt.%, based on the mass of the cleaning composition.

Bleach activators in the present invention, the bleach activator is selected from the group consisting of metal-containing bleach catalysts, such as copper ions, iron ions, manganese ions, titanium ions, tungsten ions, molybdenum ions, and mixtures thereof. If bleach activators are used, these bleach activators are generally present in an amount of from 0.1 to 15 wt.%, preferably from 0.5 to 15 wt.%, based on the mass of the detergent composition.

Clay and soil removal/anti-redeposition agents in the present invention, the clay and soil removal/anti-redeposition agents are selected from the group consisting of maleic acid-acrylic acid polymers, carboxymethyl cellulose, hydroxyethyl cellulose, and mixtures thereof. If clay and soil removal/anti-redeposition agents are used, these are typically present in an amount of 0.1 to 15 wt%, preferably 0.2 to 10 wt% of the cleaning composition by mass.

Whitening agent in the present invention, said whitening agent is selected from fluorescent whitening agents, preferably CBS-X. If whitening agents are used, the content of these whitening agents is generally 0.01 to 10 wt%, preferably 0.1 to 3 wt%, based on the mass of the cleaning composition.

[ suds suppressor ] in the present invention, the suds suppressor is selected from silicone defoamers. If suds suppressors are used, these suds suppressors are generally present in an amount of from 0.001 to 10 wt%, preferably from 0.005 to 3 wt%, based on the weight of the cleaning composition.

[ vehicle ] in the present invention, the vehicle is selected from the group consisting of polar solvents including, but not limited to, water, ethylene glycol, propylene glycol, polyethylene glycol, glycerol, and/or non-polar solvents including, but not limited to, mineral oil, silicone oil, paraffin oil, and mixtures thereof. If carriers are used, these carriers are generally present in an amount of 0.1 to 15 wt.%, preferably 1 to 15 wt.%, based on the mass of the cleaning composition.

Hydrotrope in the present invention, the hydrotrope is selected from short chain alcohols. If hydrotropes are used, these are generally present in an amount of 0.1 to 15 wt%, preferably 1 to 15 wt%, based on the weight of the cleaning composition.

Rheology modifier in the present invention, the rheology modifier is selected from the group consisting of acrylic acid polymers, acrylic acid-maleic acid polymers, xanthan gum and guar gum, and mixtures thereof. If rheology modifiers are used, these are generally present in an amount of 0.1 to 15 wt.%, preferably 0.1 to 5 wt.%, based on the weight of the cleaning composition.

Skin active agent in the present invention, the skin active agent is selected from the group consisting of vitamins, peptides, sugar amines, non-vitamin antioxidants and radical scavengers, and mixtures thereof. If skin activators are used, these are generally present in an amount of 0.01 to 15 wt.%, preferably 0.1 to 15 wt.%, based on the mass of the cleansing composition.

Processing aid in the present invention, the processing aid is selected from the group consisting of water, aggregation inhibitors (e.g. divalent salts), particulate suspension polymers (e.g. xanthan gum, guar gum, carboxymethyl cellulose). If processing aids are used, these are generally present in an amount of 0.1 to 25 wt.%, preferably 1 to 15 wt.%, based on the mass of the cleaning composition.

[ preparation of detergent ]

As described above, the present invention provides a method for producing a liquid or solid detergent.

In a preferred embodiment of the present invention, the preparation method of the liquid detergent specifically comprises: under the condition of stirring, sequentially adding all the components in the cleaning composition into deionized water, properly heating if the dissolution speed of the components is too slow, adjusting the pH of the mixed solution to 5.5-9.0 after all the components are completely dissolved, adding deionized water to 100 wt% of the rest, and uniformly stirring to obtain the liquid cleaning agent.

In a preferred embodiment of the present invention, the preparation method of the powdery or granular detergent specifically comprises: stirring, mixing and grinding a surfactant, an optional functional auxiliary agent and a filling material in the cleaning composition to prepare slurry with the solid content of 50-60 wt%, taking a small amount of the slurry, diluting the slurry with water to 100 times to obtain a 1 wt% slurry solution, adjusting the pH of the slurry solution to 9-11, sieving turbid liquid by a sieve with a certain mesh number, then carrying out spray drying and sieving, and finally adding microcapsules to be uniformly mixed to obtain the powdery cleaning agent.

In a preferred embodiment of the present invention, the preparation method of the block-shaped detergent specifically comprises: stirring, mixing and grinding a surfactant, an optional functional auxiliary agent and a filling material in the cleaning composition to prepare slurry with the solid content of 50-60 wt%, taking a small amount of the slurry, diluting the slurry by water to 100 times to obtain a 1 wt% slurry solution, adjusting the pH of the slurry solution to 9-11, sieving turbid liquid, adding microcapsules, uniformly mixing, and curing and forming to obtain the block-shaped cleaning agent.

[ application of the microcapsules and cleaning compositions of the present invention ]

The invention also provides the application of the microcapsule, and the microcapsule can be applied to the preparation of cleaning compositions.

Preferably, the microcapsules are added to the cleaning composition.

Preferably, the microcapsule is a perfume microcapsule, an insect repellent microcapsule, an antimicrobial microcapsule, a perfume/insect repellent microcapsule, a perfume/antimicrobial microcapsule, an insect repellent/antimicrobial microcapsule or a perfume/insect repellent/antimicrobial microcapsule.

The invention further provides application of the microcapsule, and the microcapsule can be applied to preparation of a cleaning agent.

Preferably, the microcapsules are added to the detergent.

The invention also provides application of the cleaning composition, and the cleaning composition can be applied to preparation of cleaning agents.

Preferably, the cleaning composition includes, but is not limited to, fabric cleaners, dish cleaners, floor cleaners, carpet cleaners, skin cleaners, hair cleaners, deodorants, and the like.

Preferably, the cleaning composition comprises perfume microcapsules, insect repellent microcapsules, antimicrobial microcapsules, perfume/insect repellent microcapsules, perfume/antimicrobial microcapsules, insect repellent/antimicrobial microcapsules or perfume/insect repellent/antimicrobial microcapsules.

The invention further provides for the use of said cleaning agent as a fabric cleaning agent, a dish cleaning agent, a floor cleaning agent, a carpet cleaning agent, a skin cleaning agent, a hair cleaning agent, a deodorant agent, and the like.

According to the invention, the fabric is of various materials, preferably of polyester fibre-containing material or of cotton fibre-containing material.

According to the invention, the cleaning agent can enhance the fragrance retention capability and make the fragrance of the fabric lasting.

According to the invention, the cleaning agent can be used for repelling mosquitoes.

According to the invention, the cleaning agent can be used for inhibiting microorganisms.

[ concrete operation of Performance test ]

1. Fragrance retention property test

Directly adding microcapsule with fragrance and/or special odor and/or special function into anionic surfactant or mixture of anionic surfactant and surfactant except cationic surfactant prepared by conventional process to obtain cleaning composition, and preparing into liquid or solid detergent.

The towel or cloth piece was treated with the prepared detergent and the fragrance-retaining property of the towel or cloth piece was evaluated at the drying stage (before and after rubbing), and the results were compared with reference samples of a detergent prepared from a cleaning composition to which no microcapsules were added and a detergent prepared from a cleaning composition to which a core material having fragrance and/or a specific odor and/or a specific function was separately added to test the fragrance-retaining effect of the resulting detergent containing microcapsules to confirm the properties.

The experiment of treating towels with the cleaning agent is carried out in a stainless steel basin or a plastic basin, each cleaning agent sample is respectively prepared into 0.2 wt% of test solution 2L by using 250mg/kg of hard water, the test solution is poured into the corresponding stainless steel basin or plastic basin, two white cotton towels with the area of 20cm by 20cm and the mass of 50g and two white polyester cloth pieces with the area of 20cm by 20cm and the mass of 25g are added, the towels and the cloth pieces are simultaneously rubbed by hands for ten times and soaked for ten minutes, and then the cotton towels and the polyester cloth pieces are spin-dried by a rinsing device; then, adding 3L of hard water of 250mg/kg into the basin, adding a spin-dried cotton towel and a spun-dried polyester cloth piece, simultaneously rubbing and washing the towel and the cloth piece for ten times by hands, and then spin-drying by a rinsing device to finish a rinsing procedure; the above rinsing procedure was repeated once more and then hung to air at room temperature.

After one week of hanging, the fragrance retention of the aired towels and sheets was evaluated and scored by 10 professional evaluation personnel. To evaluate the fragrance of the dry towels and the dry cloth pieces, each person evaluating was provided with two cotton towels and two polyester cloth pieces (1 piece each and 4 pieces each for the reference and example) to smell the towels and cloth pieces and identify which towel and cloth pieces had stronger fragrance, and then the person evaluating held both sides of the towel or cloth pieces with both hands, rubbed the cotton towels or polyester cloth pieces back and forth hard for 5 times, and operated both towels evaluated in this way. Then let the personnel of appraising smell the towel and the position of rubbing on the cloth and discern which piece of cotton towel fragrance is stronger, and which piece of polyester cloth fragrance is stronger, record their reaction again, the score is selected between 1 ~ 5, and the higher the score is the fragrant effect of leaving is better. And (3) hanging the other half of the towel or cloth piece which is treated by the cleaning agent and does not participate in evaluation after hanging for one week for three weeks, and allowing the corresponding evaluation personnel to perform evaluation again and make a record according to the method at the fourth week. The differences and trends of the fragrance retention after one-week suspension and four-week suspension are similar, so the evaluation results of the fragrance retention performance in the following examples, reference examples and comparative examples are shown only after one-week suspension.

2. Evaluation of stain Release Performance

2.1 detergency test

The detergency test is carried out on the embodiment according to the test standards of the detergency and the cycle cleaning performance of the detergent for clothes in GB/T13174-2008. the used instruments and reagents are all the specifications required in the national standard, and the used polluted cloth is JB-01 (carbon black oil polluted cloth), JB-02 (protein polluted cloth) and JB-03 (sebum polluted cloth), and is cut into the size of 6cm multiplied by 6cm before use.

The decontamination cleaning experiment is carried out in a vertical decontamination machine, before measurement, the stirring impeller, the working tank and the decontamination bathtub are numbered and fixed one by one to form a 'working unit', and are preheated to about 30 ℃ together for a period of time. During the experiment, 250mg/kg of hard water is used for respectively preparing 1L of test solution with 0.2 wt% of each cleaning composition sample, the test solution is added into a corresponding decontamination bathtub, the decontamination bathtub is placed in a corresponding position and is provided with a stirring impeller, an instrument is adjusted to stably keep the cleaning experiment at about 30 ℃, each group of decontamination cloth test pieces for measuring the whiteness before washing are respectively put into each decontamination bathtub, the stirring is started, the stirring speed is kept at 120r/min, and the cleaning process is stopped after the cleaning process lasts for 20 min. And taking out and combining the washed dirty cloth test pieces, putting the combined dirty cloth test pieces into a rinser, rinsing the combined dirty cloth test pieces twice by using tap water, taking out the test pieces after dehydration, hanging and airing the test pieces at room temperature, and measuring the whiteness after washing.

2.2 whiteness measurement

And (3) respectively assembling the test pieces into six groups with similar average blackness according to categories, wherein each group of test pieces is at least 4, numbering records are made, and each group of test pieces is used for testing the performance of one sample. Test pieces were stacked in the same order, and the whiteness values before and after cleaning were read one by one at 457nm with a whiteness meter. Taking two points on the front and back surfaces of the test piece (the two points on each surface are centrosymmetric), measuring the whiteness value, and taking the average value of four measurements as the whiteness F1 before washing of the test piece; the whiteness of the test piece after washing was measured at two points on each of the front and back surfaces of the test piece after washing, and the average of the four measurements was used as the whiteness of the test piece after washing F2.

2.3 evaluation of detergency

And (3) testing the whiteness value of the soiled cloth washed before washing, and calculating the whiteness difference A between the washed piece and the washed piece before washing (F2-F1), wherein the larger the whiteness difference A is, the higher the detergency of the detergent on the soiled cloth is, and the better the decontamination performance is.

3. Evaluation of microcapsule leakage Properties

The microcapsules may risk the leakage of the contents in the liquid detergent, for which reason we designed the following experiment to test the leakage performance of the microcapsules in the liquid detergent. Specifically, the method comprises the following steps: the method comprises the following steps of obtaining microcapsules with fragrance and/or special odor and/or special function according to the operating procedures of a fragrance retention property test, and directly adding the prepared microcapsules with fragrance and/or special odor and/or special function into an anionic surfactant or a mixture of the anionic surfactant and a surfactant except a cationic surfactant prepared according to a conventional process to obtain the cleaning composition. Taking 50mL of the cleaning composition containing the microcapsules out, placing the cleaning composition into a 50mL PET bottle, and hermetically storing the cleaning composition at 25 ℃, wherein the microcapsules are well suspended in the cleaning agent; control experiments were also performed with detergent base without microcapsules.

After 30 days of sealed storage at 25 ℃, the detergent in the PET bottle was evaluated by 5 panelists to determine whether the core material in the microcapsule particles leaked into the cleaning composition by sniffing, indicating that leakage occurred if there was fragrance, and indicating that no leakage occurred if there was no fragrance. In addition, the characteristic spectrums of four samples, such as the detergent with the microcapsules, the detergent matrix without the microcapsules, the essence solution, the detergent matrix with the essence solution and the like are analyzed by adopting High Performance Liquid Chromatography (HPLC) or Gas Chromatography (GC), and whether the clothes detergent liquid contains core substances exuded from the microcapsules is qualitatively or semi-quantitatively analyzed. Previous experiments showed that the results obtained with these two methods are consistent, so in the examples below, only the results obtained with sniffing are shown.

4. Antimicrobial Effect evaluation of antimicrobial microcapsules

The antimicrobial effect of the antimicrobial microcapsules in liquid detergents can be evaluated using preservative challenge experiments. To this end, we have designed the following experiments, in particular, according to methods known in the art (Orth, D.S.; Linear regression method for characterization of cosmetic preliminary efficacy. J.Soc.cosmetics & Toiletries,102(12),1987, 47-54.): stock solutions of three samples of a cleaning agent added with antimicrobial microcapsules (the cleaning agent matrix does not contain a preservative), a cleaning agent added with the microcapsules but does not contain the antimicrobial agent in a core material (the cleaning agent matrix does not contain the preservative), and a cleaning agent not added with any microcapsules (the cleaning agent matrix does not contain the preservative) are respectively stored at 37 ℃ for a group of samples inoculated with different strains, bacteria (escherichia coli, staphylococcus aureus and pseudomonas aeruginosa) are subjected to colony counting measurement at 0h, 2h, 4h, 6h, 24h and 168h, fungi (candida albicans and aspergillus niger) are subjected to 0h, 4h, 24h and 168h, spores (bacillus subtilis var niger) are subjected to colony counting measurement at 0h, 24h and 168h, the bacteria and the spores are cultured in a culture medium at 37 ℃ for 48h, and after yeast and mould are cultured at 25 ℃ for 72h, experimental results are observed, experimental data are recorded, and (5) solving the D value by using a linear regression method, and judging whether the anti-corrosion effect on each strain is qualified or not.

5. Evaluation of mosquito repelling effect of insect-repelling microcapsules

The insect-repellent effect of the insect-repellent microcapsules in the liquid detergent is qualitatively evaluated by a self-made method. Specifically, the method comprises the following steps: preparing a floor cleaner added with insect-repellent microcapsules, a floor cleaner added with microcapsules but not containing insect-repellent molecules in core materials, and a floor cleaner not added with any microcapsules into a diluted solution for use according to a conventional dilution multiple (160 times), after trapping food is removed in a 120-square-meter empty room in which 50-100 cockroaches are trapped in advance, equally dividing the room into a left area, a middle area and a right area which are consistent in light intensity and temperature and humidity, and cleaning the floor by using the diluted solution of the floor cleaner respectively, wherein the middle area (an implementation group area) is cleaned by using the diluted solution of the floor cleaner added with the insect-repellent microcapsules, and the left area and the right area (a reference group area) are cleaned by using the other two diluted solutions respectively; after cleaning, waiting for the floor to dry, and in order to promote accelerated release of the core material in the microcapsules left on the floor in the experimental group area, a certain number of people can choose to wear flat shoes and arrange the flat shoes on the floor in the experimental group area in the room to go and back for 3 times; all people are then evacuated, lights and doors and windows are closed, distribution of cockroaches in a room is observed and counted for 12h, 48h and 72h, and if no cockroaches gather in an implementation group area (less than 5% of the total number of cockroaches) cleaned by the floor cleaner added with the insect-repellent microcapsules, or the number of cockroaches in the implementation group area is obviously less than that in a reference group area (less than 10% of the total number of cockroaches in the reference group), the insect-repellent microcapsules are considered to be effective in repelling the cockroaches.

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the description of the present invention, and such equivalents also fall within the scope of the invention.

Preparing microcapsules: a single perfume or a mixed perfume, an insect repellent or mosquito repellent, an antimicrobial agent was dissolved in dipropylene glycol or propylene glycol at 6.25 wt% with respect to the mass of the whole microcapsule to form a core material solution, wherein the mass of the above organic solvent was 18.75 wt% with respect to the mass of the whole microcapsule, that is: the hollow polymer microspheres in the microcapsule account for 75 wt% of the total microcapsule mass, the first substance in the core substance in the microcapsule accounts for 6.25 wt% of the total microcapsule mass, and the organic solvent in the core substance accounts for 18.75 wt% of the total microcapsule mass. Mixing the core substance solution with hollow polymer microspheres with micro-channels on the surfaces under negative pressure, soaking and settling; separating the settled microspheres, and cleaning the surfaces of the microspheres by using ethanol to obtain the microcapsules with fragrance and/or special odor and/or special functions. The microcapsules are stored in water for later use.

Preparation of liquid detergent: adding a certain amount of deionized water into a reaction tank, adding the components in the formula table according to a certain sequence under stirring, properly heating if the dissolution speed of the components is too low, adjusting the pH of the mixed solution to 7.0-9.0 after the components are added, adding deionized water to 100 wt%, and uniformly stirring to obtain the liquid detergent.

Preparation of a powdery detergent: adding the components in the formula table into a reaction tank, stirring, uniformly mixing, grinding by using a colloid mill to prepare slurry with the solid content of 50-60 wt%, taking a small amount of the slurry, diluting to 100 times by using water to obtain a 1 wt% slurry solution, adjusting the pH of the slurry solution to 9-11, sieving turbid liquid by using a sieve with a certain mesh number, then carrying out spray drying and sieving, and finally adding microcapsules to obtain the powdery detergent.

Examples 1 to 6

Taking a fabric cleaning agent as an example, the comprehensive performances of the fabric cleaning agent added with essence microcapsules, such as stain removal performance, fragrance retention performance and the like, are considered, formula tables and performance test results of examples 1 to 6 are shown in tables 1 and 2, the microcapsules are hollow polymer brittle microspheres or elastic microspheres with micro-pores on the surfaces, essence wrapped by the microcapsules is phenethyl alcohol with the ClogP value of less than 3.4, and the phenethyl alcohol has rose fragrance.

TABLE 1 component content and stain removal Performance for examples 1-6

TABLE 2 evaluation of fragrance remaining in examples 1 to 6

Examples 7 to 12

Taking a fabric cleaner as an example, the comprehensive performances of the fabric cleaner added with essence microcapsules, such as decontamination performance, fragrance retention performance and the like, are considered, formula tables and performances of examples 7-12 are shown in tables 3 and 4, the microcapsules are hollow polymer brittle microspheres or elastic microspheres with micro channels on the surfaces, the essence wrapped by the microcapsules is hexyl cinnamaldehyde with a ClogP value larger than 3.4, and the hexyl cinnamaldehyde is a light yellow liquid and has jasmine fragrance.

TABLE 3 component contents and stain removal Properties of examples 7-12

TABLE 4 evaluation of fragrance remaining in examples 7 to 12

Examples 13 to 18

Taking a fabric cleaning agent as an example, the comprehensive performances of the fabric cleaning agent added with essence microcapsules, such as decontamination performance, fragrance retention performance and the like, are considered, formula tables and performances of examples 13-18 are shown in tables 5 and 6, the microcapsules are hollow polymer brittle microspheres or elastic microspheres with micro-pores on the surfaces, the essence wrapped by the microcapsules is prepared from hexyl cinnamaldehyde with a ClogP value of more than 3.4 and phenethyl alcohol with a ClogP value of less than 3.4, and the essence A is prepared from 67% of hexyl cinnamaldehyde perfume and 33% of phenethyl alcohol perfume according to mass percentage and is used for providing fresh rose fragrance.

TABLE 5 component contents and stain removal Properties of examples 13-18

TABLE 6 evaluation of fragrance remaining in examples 13 to 18

Examples 19 to 25

Taking a fabric cleaning agent as an example, the comprehensive performances of the fabric cleaning agent added with the essence microcapsules, such as decontamination performance, fragrance retention performance and the like, are examined, formula tables and performances of examples 19-25 are shown in tables 7 and 8, and the microcapsules are hollow polymer brittle microspheres or elastic microspheres with micro-pores on the surfaces, or a mixture of the brittle microspheres and the elastic microspheres. The essence wrapped by the microcapsule is directly a flower and fruit fragrant essence solution B which is prepared from various spices and diluted by a solvent and provided by a certain essence company, and the essence B has orchid fragrance.

TABLE 7 component contents and stain removal Properties of examples 19 to 25

TABLE 8 evaluation of fragrance remaining in examples 19 to 25

Examples 26 to 33

Taking a fabric cleaning agent as an example, the comprehensive performances of the fabric cleaning agent added with the essence microcapsules, such as stain removal performance, fragrance retention performance and the like, are examined, the formula table and performances in examples 26-33 are shown in tables 9-12, the microcapsules are hollow polymer brittle microspheres or elastic microspheres with micro-pores on the surfaces, or a mixture of the brittle microspheres and the elastic microspheres, the essence wrapped by the microcapsules is a flower and fruit fragrance essence solution B which is provided by a certain essence company and prepared from various spices through dilution by solvents, and the essence B is partial to orchid fragrance.

TABLE 9 component contents and stain removal Properties of examples 26 to 29

TABLE 10 evaluation of fragrance remaining in examples 26 to 29

TABLE 11 compositions and soil release Properties of examples 30 to 33

TABLE 12 evaluation of fragrance remaining in examples 30 to 33

Examples 34 to 40

Taking a fabric cleaning agent as an example, the comprehensive performances of the clothes cleaning agent (without adding a preservative into a substrate) added with the antimicrobial microcapsules and/or the essence microcapsules are considered, the formula tables and performances in examples 34-40 are shown in tables 13-14, the microcapsules are hollow polymer brittle microspheres or elastic microspheres with micro-pores on the surfaces, or a mixture of brittle microspheres and elastic microspheres, the antimicrobial agent is 5-chloro-2-methyl-4-isothiazoline-3-ketone, the essence in the essence microcapsule is essence B, it is possible to try to accelerate the release of a portion (e.g. crushing) of the core material in the laundry detergent microcapsule onto the microbial culture medium, the microcapsule is used for simulating the process that microcapsules remained on the fabric are squeezed or rubbed to break and release the core material during the movement of a human body.

TABLE 13 component content and stain removal Performance for examples 34-40

TABLE 14 evaluation of antimicrobial Properties of examples 34-40

Examples 41 to 45

Taking the floor cleaner as an example, the comprehensive performances such as decontamination performance, insect repelling performance and the like of the floor cleaner (substrate is not added with insect repelling components) added with insect repelling microcapsules and/or essence microcapsules are examined, the formula table and performances in examples 41-45 are shown in tables 15-16, the microcapsules are hollow polymer brittle microspheres or elastic microspheres with micro-pores on the surface or a mixture of the brittle microspheres and the elastic microspheres, the insect repellent is DEET, and the essence in the essence microcapsules is essence B.

TABLE 15 component contents and soil release Properties of examples 41 to 45

TABLE 16 evaluation of insect-repellent Properties of examples 41 to 45

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A microcapsule for a cleaning composition, the microcapsule comprising hollow polymeric microspheres and a substance contained in the microspheres; the substance contained in the microspheres comprises a substance having a fragrance and/or having a specific odor and/or having a specific function; in addition, the hollow polymer microspheres are hollow microspheres, the shell layers are crosslinked polymers, the particle size of the microspheres is 1-250 micrometers, and the thickness of the shell layers is 0.01-10 micrometers; wherein the surface of the microsphere is provided with micro channels, and the pore diameter of the micro channels is less than or equal to 0.05 micron;

the above "substance contained in the microspheres" is referred to as "core substance", and the above "substance having a fragrance and/or a specific odor and/or a specific function" is referred to as "first-type substance";

the shell layer of the hollow polymer microsphere with the micro-channels on the surface is an elastic shell layer consisting of cross-linked polymers, and the polymerized monomers forming the cross-linked polymers in the elastic shell layer comprise a monomer A, a monomer B and a monomer C; the monomer A is a monomer for making the crosslinked polymer brittle and comprises one or more of styrene, methyl methacrylate and methyl acrylate; the monomer B is a monomer for imparting elasticity to the crosslinked polymer and comprises methacrylic acid C₄Alkyl esters, acrylic acid C₄Alkyl esters, including C₄Isomers of alkyl groups selected from n-butyl methacrylate and n-butyl acrylate; the monomer C is a monomer for adjusting the elasticity and/or brittleness of the cross-linked polymer; the monomer C comprises one or two of ethyl methacrylate and ethyl acrylate; the crosslinked polymer comprises, by weight, a monomer A accounting for more than or equal to 30 wt% and less than 70 wt% of the mass of the polymer, a monomer B accounting for more than or equal to 30 wt% and less than 70 wt% of the mass of the polymer, and a monomer C accounting for more than 0 and less than or equal to 60 wt% of the mass of the polymer;

the first class of substances includes one or more of the following: substances with fragrance: spices, essences; substances with a special odor; substances with special functions: mosquito repellent, insect repellent, antimicrobial;

the microcapsule is prepared by the following method:

mixing hollow microspheres with micro channels with a core substance under negative pressure, soaking, settling and separating, wherein the core substance is extruded into the hollow microspheres through the micro channels of the hollow microspheres under negative pressure, thus preparing the microcapsule.

2. A microcapsule according to claim 1, characterized in that said first type of substance comprises one, two or three of the following three groups of substances: (1) one or more of a fragrance, an essence, or a substance having a specific odor; (2) one or more of mosquito repellent and insect repellent; (3) an antimicrobial agent.

3. A microcapsule according to claim 2, characterized in that said first type of substance comprises one, two or three of the following three groups of substances in percentages by mass:

(1) one or more of spices, essence or substances with special odor accounts for 0-100 wt% of the first substance by mass percent;

(2) one or more of mosquito repellent and insect repellent accounts for 0-100 wt% of the first substance;

(3) the antimicrobial agent accounts for 0 to 100 weight percent of the first substance;

4. A microcapsule according to claim 3, characterized in that said first type of substance comprises one, two or three of the following three groups of substances in percentages by mass:

(1) one or more of spices, essence or substances with special odor accounts for 0.01-100 wt% of the first substance by mass percent;

(2) one or more of mosquito repellent and insect repellent accounts for 0.01-100 wt% of the first substance;

(3) the antimicrobial agent accounts for 0.01 to 90 weight percent of the first substance;

5. A microcapsule according to claim 4, characterized in that said first type of substance comprises one, two or three of the following three groups of substances in percentages by mass:

(1) one or more of spices, essence or substances with special odor accounts for 0.1-100 wt% of the first substance by mass percent;

(2) one or more of mosquito repellent and insect repellent accounts for 0.1-100 wt% of the first substance;

(3) the antimicrobial agent accounts for 0.1 to 80 weight percent of the first substance;

6. Microcapsules according to claim 1, characterized in that the first type of substance, independent of the functional groups, the octanol water partition coefficient ClogP, the polarity, the water solubility, is selected from components of a single chemical structure, or mixtures of more than one component.

7. Microcapsules according to claim 6, characterized in that the odoriferous substance and the substance with a characteristic odour are a mixture of odoriferous substances having an octanol water partitioning coefficient ClogP of 3.4 or more and odoriferous substances having an octanol water partitioning coefficient ClogP of less than 3.4 and odoriferous substances.

8. Microcapsules according to claim 7, characterized in that the odoriferous and odor-specific substances are selected from one or more of odoriferous and odor-specific substances having an octanol water partition coefficient ClogP of greater than or equal to 3.4, from one or more of odoriferous and odor-specific substances having an octanol water partition coefficient ClogP of less than 3.4, and from a combination of one or more of odoriferous and odor-specific substances having an octanol water partition coefficient ClogP of greater than or equal to 3.4 and one or more of odor-specific and odor-specific substances having an octanol water partition coefficient ClogP of less than 3.4.

9. A microcapsule according to claim 8, characterized in that said odoriferous and odor-specific substances are selected from one or more of the group consisting of phenethyl alcohol, hexyl cinnamic aldehyde, levo citronellol, dextro citronellol, terpineol, hydroxycitronellal, lilial, linalool, geraniol, vanillin, ethyl acetate, ethyl acetoacetate, benzyl acetate, dihydromyrcenol, ethylhexyl cinnamaldehyde, benzyl propionate and g-n-ionone.

10. The microcapsule of claim 1, wherein the mosquito and insect repellent is selected from DEET, Icaritin, anophelate, menthol, essential oil of Artemisia annua, essential oil of Eucalyptus globulus, and oil of Melia azedarach.

11. The microcapsules of claim 10, wherein the insect repellent microcapsules selected from the group consisting of delphene which is highly effective in repelling mosquitoes are used as floor cleaners, and the insect repellent microcapsules selected from the group consisting of icaritin, Icaridin, which is non-irritating to the skin, are used as skin surface cleaners.

12. A microcapsule according to claim 1, characterized in that said antimicrobial agent is selected from at least one of isothiazolinone derivatives, parabens, 1, 2-benzisothiazolin-3-one, hexachlorophene and sodium hydroxymethylglycinate.

13. Microcapsules according to claim 12, characterized in that they are chosen from isothiazolinone derivatives for use as antimicrobial microcapsules in detergents.

14. A microcapsule according to claim 12, characterized in that said isothiazolinone derivative is selected from at least one of 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one; the nipagin is at least one of methyl parahydroxybenzoate, ethyl parahydroxybenzoate, propyl parahydroxybenzoate, butyl parahydroxybenzoate and isobutyl parahydroxybenzoate.

15. A microcapsule according to any one of claims 1 to 14, characterized in that the core material further comprises other substances, denoted "second type substances", including one or more of drugs, chromogens, dyes, pigments, flavourings, waxes, silicone oils, emollients, vitamins, fats, enzymes, mould inhibitors, binders, phase change materials and flavourings.

16. A microcapsule according to any one of claims 1 to 14, characterized in that the core material further comprises an organic solvent, said organic solvent being uniformly mixed with the first type of material and optionally the second type of material and then encapsulated together in the microcapsule; the "second class of substances" includes one or more of drugs, chromogens, dyes, pigments, flavors, waxes, silicone oils, emollients, vitamins, fats, enzymes, mold inhibitors, adhesives, phase change materials, and odorants.

17. A microcapsule according to claim 16, characterized in that the added amount of said organic solvent is kept at the minimum amount required to provide a homogeneous solution of the first type of substance and optionally the second type of substance, and a suitable amount to adjust the microcapsule density.

18. A microcapsule according to any one of claims 1 to 14, characterized in that the first substance is present in an amount of 0.01 to 100% by mass of the core substance.

19. A microcapsule according to claim 18, wherein the first substance is present in an amount of 0.1 to 90% by mass of the core substance.

20. A microcapsule according to claim 19, wherein the first substance is present in an amount of 0.3 to 80% by mass of the core substance.

21. A microcapsule according to claim 15, characterized in that the second substance is present in an amount of 0% to 99.99% by mass of the core substance.

22. A microcapsule according to claim 21, wherein the second species is present in an amount of from 0.1 to 90% by mass of the core material.

23. A microcapsule according to claim 22, wherein the second species is present in an amount of from 0.3 to 80% by mass of the core material.

24. A microcapsule according to claim 16, wherein the organic solvent is present in an amount of 0 to 99.99% by mass of the core material.

25. A microcapsule according to claim 24, wherein the organic solvent is present in an amount of 9.9 to 99.8% by mass of the core material.

26. A microcapsule according to claim 25, wherein the organic solvent is present in an amount of 19.7 to 99.4% by mass of the core material.

27. A microcapsule according to claim 1, wherein the hollow polymeric microspheres have a particle size of 2 to 100 microns.

28. A microcapsule according to claim 27, wherein the hollow polymeric microspheres have a particle size of 3 to 30 microns.

29. The microcapsule according to claim 1, wherein the shell thickness of the hollow polymeric microspheres is 0.1 to 10 μm.

30. A microcapsule according to claim 1, characterized in that the pore size of the microchannels of the hollow polymeric microspheres is equal to or less than 0.03 μm.

31. A microcapsule according to claim 30, wherein the pore size of the microchannels of the hollow polymeric microspheres is 0.02 μm or less.

32. The microcapsule according to claim 1, wherein the hollow polymer microspheres account for 1 to 99.9 wt% of the mass of the microcapsule; the core substance accounts for 0.1-99 wt% of the microcapsule by mass.

33. A microcapsule according to claim 32, wherein the hollow polymeric microspheres are present in an amount of 20 to 99 wt% based on the mass of the microcapsule; the core substance accounts for 1-80 wt% of the microcapsule by mass.

34. The microcapsule according to claim 33, wherein the hollow polymeric microspheres account for 50 to 95 wt% of the mass of the microcapsule; the core substance accounts for 5-50 wt% of the microcapsule by mass.

35. A process for the preparation of microcapsules according to any one of claims 1 to 34, characterized in that it comprises: mixing hollow microspheres with micro channels with a core substance under negative pressure, extruding the core substance into the hollow microspheres through the micro channels of the hollow microspheres under the negative pressure, soaking, settling and separating to obtain the microcapsule.

36. The method of claim 35, wherein the negative pressure is less than 101 kPa.

37. The method of claim 36, wherein the pressure is less than 10 kPa.

38. The method of claim 35, further comprising cleaning the separated microcapsules with a lower alcohol, an aqueous solution or a mixture thereof to wash off the core material from the surface of the microspheres.

39. The method of claim 38, wherein the lower alcohol is C_1-6An alkyl alcohol.

40. The method of claim 39, wherein the lower alcohol is methanol, ethanol, propanol, or butanol.

41. The preparation method of claim 35, wherein the mass charge ratio of the hollow microspheres with microchannels to the core material is 1000-0.01: 1.

42. The method of claim 35, wherein the prepared microcapsule is stored in water or an aqueous solution containing a surfactant and stored at room temperature or low temperature.

43. The method for preparing according to claim 35, wherein the method comprises the following steps:

44. The method of claim 43, wherein the method of preparing the microcapsule comprises the steps of:

a') placing hollow microspheres with micro-channels in a single-opening glass container with an air extraction joint, mixing the first type of substance and optionally the second type of substance with an organic solvent to form a liquid core substance, placing the liquid core substance in a constant-pressure dropping funnel, assembling the constant-pressure funnel and the single-opening glass container, connecting a vacuum air extraction device, and extracting air for 5-120 minutes; under the negative pressure lower than 30kpa, opening a constant-pressure funnel switch to mix, soak and settle core substances in the funnel and microspheres in the container;

b') separating the settled microspheres, and cleaning the surfaces of the microspheres by using ethanol or water or a mixed solution of the ethanol and the water to obtain the microcapsules.

45. A cleaning composition characterized in that the composition comprises the following components by mass: 5 to 90 wt% of a surfactant, 0.01 to 10 wt% of a microcapsule according to any one of claims 1 to 34.

46. The cleaning composition as claimed in claim 45, wherein the composition comprises the following components by mass: 12-75 wt% of surfactant and 0.1-8 wt% of the microcapsule.

47. The cleaning composition of claim 45, further comprising a functional adjunct comprising one or more of a chelating agent, a preservative, a dye, a conventional perfume, a builder, a dye transfer inhibitor, an enzyme stabilizer, a bleach activator, a brightener, a suds suppressor, a carrier, a hydrotrope, a rheology modifier, a skin activator, and a processing aid.

48. The cleansing composition of claim 47 wherein the surfactant is an anionic surfactant or a mixture of an anionic surfactant and a surfactant other than a cationic surfactant.

49. The cleansing composition of claim 48 wherein the surfactant is a mixture of anionic and nonionic surfactants, a mixture of anionic and zwitterionic surfactants, an anionic and nonionic surfactant, and a zwitterionic surfactant.

50. A cleaning agent, characterized in that the cleaning agent comprises the cleaning composition of any one of claims 45 to 49.

51. The cleaning agent as claimed in claim 50, wherein the amount of the cleaning composition added in the cleaning agent is 15-90 wt%.

52. The cleaning composition of claim 50, wherein the cleaning composition is in a liquid or solid form.

53. The cleaning agent according to claim 52, wherein when the cleaning agent is in a liquid form, the remaining component in the cleaning agent is a solvent; when the cleaning agent is in a solid state, the remaining components in the cleaning agent are fillers for molding the cleaning agent.

54. The cleaning composition as claimed in claim 50, further comprising a pH adjusting agent.

55. The cleaning agent according to claim 54, wherein the pH of the cleaning agent is 5 to 13.

56. The cleaning agent according to claim 55, wherein when the cleaning agent is in a liquid form, the pH thereof is 5.5 to 9; when the cleaning agent is solid, the pH value is 9-11.

57. Use of microcapsules according to any of claims 1 to 34 for the preparation of a cleaning composition.

58. The use according to claim 57, wherein said microcapsules are added to a cleaning composition.

59. The use of claim 58, wherein the microcapsule is a perfume microcapsule, an insect repellent microcapsule, an antimicrobial microcapsule, a perfume and insect repellent microcapsule, a perfume and antimicrobial microcapsule, an insect repellent and antimicrobial microcapsule or a perfume, an insect repellent and antimicrobial microcapsule.

60. Use of microcapsules according to any of claims 1 to 34 for the preparation of detergents.

61. The use according to claim 60, wherein said microcapsules are added to a detergent.

62. The use of claim 61, wherein the microcapsule is a perfume microcapsule, an insect repellent microcapsule, an antimicrobial microcapsule, a perfume and insect repellent microcapsule, a perfume and antimicrobial microcapsule, an insect repellent and antimicrobial microcapsule or a perfume, an insect repellent and antimicrobial microcapsule.

63. Use of the cleaning composition of any one of claims 44-49 in the preparation of a cleaning agent.

64. The use according to claim 63, wherein said cleaning composition comprises fabric cleaners, dish cleaners, floor cleaners, carpet cleaners, skin cleaners, hair cleaners and deodorants.

65. The use of claim 63, wherein the cleaning composition comprises perfume microcapsules, insect repellent microcapsules, antimicrobial microcapsules, perfume and insect repellent microcapsules, perfume and antimicrobial microcapsules, insect repellent and antimicrobial microcapsules or perfume, insect repellent and antimicrobial microcapsules.

66. Use of a cleaning agent according to any of claims 50 to 56 as a fabric cleaning agent, a dish cleaning agent, a floor cleaning agent, a carpet cleaning agent, a skin cleaning agent, a hair cleaning agent or a deodorant.

67. The use according to claim 66, wherein said cleaning agent is used to enhance fragrance retention, to provide a lasting fragrance to the fabric; the cleaning agent is used for repelling mosquitoes; the detergent is used for inhibiting microorganisms.